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WO2007136140A1 - Procédé pour évaluer les performances d'un catalyseur d'électrode pour batterie, procédé pour analyser un catalyseur d'électrode pour batterie, catalyseur d'électrode pour batterie, et batterie de piles à combustible comprenant le catalyseur d'électrode - Google Patents

Procédé pour évaluer les performances d'un catalyseur d'électrode pour batterie, procédé pour analyser un catalyseur d'électrode pour batterie, catalyseur d'électrode pour batterie, et batterie de piles à combustible comprenant le catalyseur d'électrode Download PDF

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Publication number
WO2007136140A1
WO2007136140A1 PCT/JP2007/061029 JP2007061029W WO2007136140A1 WO 2007136140 A1 WO2007136140 A1 WO 2007136140A1 JP 2007061029 W JP2007061029 W JP 2007061029W WO 2007136140 A1 WO2007136140 A1 WO 2007136140A1
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WO
WIPO (PCT)
Prior art keywords
electrode catalyst
catalyst
fuel cell
area
specific surface
Prior art date
Application number
PCT/JP2007/061029
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English (en)
Japanese (ja)
Inventor
Hirofumi Iisaka
Original Assignee
Toyota Jidosha Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyota Jidosha Kabushiki Kaisha filed Critical Toyota Jidosha Kabushiki Kaisha
Priority to EP07744440A priority Critical patent/EP2031678A1/fr
Priority to US12/299,990 priority patent/US20090117450A1/en
Publication of WO2007136140A1 publication Critical patent/WO2007136140A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/10—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using catalysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04305—Modeling, demonstration models of fuel cells, e.g. for training purposes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a battery electrode catalyst performance evaluation method, a search method, a fuel cell electrode catalyst with a small overvoltage found by the search method and excellent power generation performance, and the electrode
  • the present invention relates to a fuel cell having a catalyst.
  • Fuel cells are attracting attention as a clean power generation system with the product of the cell reaction being water in principle and having almost no adverse effect on the global environment.
  • a polymer electrolyte fuel cell has a pair of electrodes on both sides of a proton-conducting solid polymer electrolyte membrane, supplies hydrogen gas to one electrode (fuel electrode: anode), and oxygen gas.
  • fuel electrode anode
  • oxygen gas oxygen gas
  • air is supplied as an oxidizing agent to different electrodes (air electrode: cathode) to obtain an electromotive force.
  • the polymer electrolyte fuel cell has (1) the development of a polymer electrolyte membrane having high ionic conductivity, and (2) coating with an ion exchange resin (polymer electrolyte) that is the same or different from the polymer electrolyte membrane.
  • an ion exchange resin polymer electrolyte
  • the catalyst-supported carbon as a constituent material for the electrode catalyst layer, the so-called three-dimensional reaction size in the catalyst layer can be achieved, and the battery characteristics have improved dramatically.
  • solid polymer fuel cells are used for mobile vehicles such as electric vehicles and power sources for small cogeneration systems. Is expected to be put to practical use.
  • a gas diffusible electrode used in a polymer electrolyte fuel cell includes a catalyst layer containing catalyst-supported carbon coated with the above ion exchange resin, and supplies a reaction gas to the catalyst layer and supplies electrons. It consists of a gas diffusion layer that collects current. In the catalyst layer, minute amounts formed between secondary particles or tertiary particles of carbon as a constituent material. There are voids made up of fine pores, and these voids function as reaction gas diffusion channels.
  • a noble metal catalyst such as platinum or platinum alloy which is stable in an ion exchange resin is usually used.
  • a catalyst in which a noble metal such as platinum or a platinum alloy is supported on carbon black has been used.
  • Platinum-supported carbon black is obtained by adding sodium hydrogen sulfite to a chloroplatinic acid aqueous solution and then reacting with hydrogen peroxide solution. The resulting platinum colloid is supported on carbon black, washed, and if necessary. In general, it is prepared by heat treatment.
  • the electrode of a polymer electrolyte fuel cell is manufactured by preparing platinum by dispersing platinum-supported carbon black in a polymer electrolyte solution, applying the ink to a gas diffusion substrate such as carbon paper, and drying. The A polymer electrolyte membrane is sandwiched between these two electrodes and hot-pressed to assemble an electrolyte membrane-one electrode assembly (MEA).
  • MEA electrolyte membrane-one electrode assembly
  • the total pore volume of pores with a specific surface area and less than 2 nm in diameter is greater than or equal to 0.8 cm 3 Z g, and the pore volume occupied by pores less than 2 nm in diameter is the total pore
  • An electrode catalyst for a fuel cell is disclosed in which the amount of catalyst supported is 60% or more of the volume and is defined as 5 to 70% by mass of the entire particle.
  • the electrode catalyst is defined by the average particle diameter, specific surface area, pore volume and catalyst mass with respect to the support.
  • the problem is that there is no provision for overvoltage. It is considered that overvoltage cannot be defined because it is defined not by the physical properties of the catalyst but by the physical properties of the support (specific surface area, etc.) and not by the experimental values obtained by electrochemistry.
  • a hydrogen-containing gas (fuel gas) is used as an anode reaction gas
  • an oxygen-containing gas such as air
  • the electrode reaction shown in the following equation (1) at the anode and the following equation (2) at the force sword proceed, respectively, and the overall battery reaction shown in the equation (3) progresses as a whole. Electromotive force is generated.
  • Japanese Patent Laid-Open No. 2002-15744 discloses a metal catalyst selected from the group consisting of platinum and a platinum alloy in a force sword catalyst layer for the purpose of obtaining excellent battery sword polarization characteristics and high battery output.
  • the polarization characteristics in the force sword are improved by including a metal complex having a predetermined amount of iron or chromium.
  • a solid polymer fuel cell comprising an anode, a force sword, and a polymer electrolyte membrane disposed between the anode and the force sword, wherein the force sword includes a gas diffusion layer, A catalyst layer disposed between the gas diffusion layer and the polymer electrolyte membrane, the noble metal catalyst selected from the group consisting of platinum and a platinum alloy, and a metal complex containing iron or chromium.
  • the solid polymer fuel cell is characterized in that it is contained in the layer and the metal complex is contained in an amount of 1 to 40 mol% of the total amount of the metal complex and the noble metal catalyst.
  • the metal complex having iron or chromium contained in the catalyst layer of the cathode can effectively reduce the activation overvoltage of the oxygen reduction reaction of the cathode represented by the formula (2). According to the report, the polarization characteristics of the force sword are improved, and high battery output can be obtained. Disclosure of the invention
  • Electrocatalysts and fuel cells that use them have been tried to be used for automobiles and stationary power supplies, and improving battery performance is important. There is a strong demand to maintain performance. In addition, the performance requirements are particularly strong because of the use of expensive precious metals. In particular, since the oxygen reduction overvoltage is large at the oxygen reduction electrode, the dissolution and reprecipitation of platinum is the main cause of lowering the fuel cell efficiency in a high potential environment.
  • the present invention develops a method for accurately evaluating the performance of the fuel cell electrode catalyst, searches for a fuel cell electrode catalyst having excellent performance, and further searches for a novel fuel cell electrode catalyst using the above method.
  • An object of the present invention is to specifically obtain an electrode catalyst for a fuel cell having excellent catalytic activity.
  • the present inventor noticed that the overvoltage largely depends on the oxide film on the surface of the catalyst metal, and in order to define the overvoltage, it is necessary to define the parameters related to the physical properties of the catalyst and the experimental values based on the electrochemistry. I thought there was. Therefore, the present invention has been achieved by expressing the degree of formation of the oxide film as a standardized specific parameter and using it as an index for evaluating the performance of the electrode catalyst for fuel cells.
  • the present invention is an invention for a method for evaluating the performance of an electrode catalyst for a fuel cell in which a catalytic metal is supported on a conductive support, wherein the voltammogram area Z catalyst specific surface area of the electrode catalyst is evaluated.
  • the voltammogram area has a specific surface area of 1.0 ⁇ 10 1 4 (mV-A-g / m 2 ) or higher.
  • the invention is a method for evaluating the performance of a fuel cell electrode catalyst in which a catalytic metal is supported on a conductive support.
  • the voltammogram area catalyst specific surface area of the catalyst metal is used as an index for the performance evaluation
  • the voltammogram area of the electrode catalyst can be obtained by voltammetry.
  • CMC carboxymethyl cellulose
  • PVDF polyvinylidene fluoride
  • the reduction current value changes, especially the oxygen reduction current value, compared to the case where Nafion (trade name), which is a polymer electrolyte, is used. It is particularly preferable to greatly emphasize the change and capture it clearly, so that the difference in the formation of the acid film can be clearly determined.
  • the present invention is an invention in which the above index is used for searching for a novel and high-performance fuel cell electrode catalyst. That is, the invention is a method for searching for an electrode catalyst for a fuel cell in which a catalytic metal is supported on a conductive support, wherein the voltammogram area Z specific surface area of the electrode catalyst is used as an index of the search, and the voltamgram area specific surface area There 1.
  • OX 10- 4 - characterized by a good or (mV a ⁇ g / m 2 ).
  • the invention also relates to a method for searching for an electrode catalyst for a fuel cell in which a catalytic metal is supported on a conductive support, wherein the voltamgram area Z catalyst specific surface area of the catalytic metal is used as an index for the search, and the voltamgram area Z ratio A surface area of 1.0 X 10 ⁇ 4 (mV ⁇ A ⁇ g / m 2 ) or more is considered good.
  • CMC carboxymethylcellulose
  • PVDF polyvinylidene fluoride
  • the present invention is an invention of an electrode catalyst specifically searched for by the method for searching for an electrode catalyst for a fuel cell. That is the invention of the catalytic metal on a conductive support is supported fuel cell electrode catalyst, voltammogram area / ⁇ catalyst ratio surface area of the electrode catalyst 1. OX 1 0- 4 (mV - A - g / m 2 ) or more. Or, an invention of the catalytic metal on a conductive support is supported fuel cell electrode catalyst, voltammogram area / catalyst specific surface area of the catalyst metal is 1. 0 X 1 0- 4 (mV ⁇ A ⁇ g / m 2 ) characterized in that it contains a catalytic metal that is greater than or equal to.
  • CMC carboxymethylcellulose
  • PVDF polyvinylidene fluoride
  • the present invention is a fuel cell using the above electrode catalyst.
  • the fuel cell of the present invention is a solid polymer fuel cell comprising an anode, a force sword, and a polymer electrolyte membrane disposed between the anode and the force sword.
  • a catalytic metal is supported on a conductive support, and the voltammogram area Z catalyst ratio table area of the electrocatalyst is 1.0 X 1 0 _ 4 (mV-A-g Xm 2 ) or more.
  • the catalytic metal on a conductive support is supported, voltammogram area Z catalyst specific surface area of the catalyst metal comprises 1.
  • Catalytic metal is 0 X 1 0- 4 (mV ⁇ A ⁇ g / m 2) or more It is characterized by this.
  • the fuel cell of the present invention comprises a flat unit cell and two separators arranged on both sides of the unit cell.
  • the electrode reaction shown in the equation (1) at the anode and the equation (2) at the power sword proceed, respectively, and as a whole the equation (3) All the battery reactions shown progress and electromotive force is generated.
  • the fuel cell of the present invention has an excellent power generation performance because it uses an electrode catalyst having a small overvoltage and a high catalytic activity.
  • the voltammogram area of the electrocatalyst obtained from the voltammetry is divided by the specific surface area of the catalyst to be used as a standard for performance evaluation and search for a new catalyst.
  • a fuel cell electrode catalyst can be accurately evaluated and searched. This greatly reduces the labor and time for fuel cell performance evaluation and search.
  • Fig. 1 schematically shows how platinum atoms on the surface of platinum particles are oxidized by oxygen molecules generated from water molecules.
  • Figure 2 shows an example of the voltammogram of a platinum catalyst.
  • Figure 3 shows the current-voltage curve and the relationship between theoretical electromotive force and overvoltage.
  • Fig. 4 shows the voltammetric results of the reduction current of platinum using Nafion, CMC, and PVDF as binders.
  • Fig. 5 compares the oxygen reduction current values of white gold at 80 OmV using Na fion (trade name), CMC, and PVDF as binders.
  • Figure 6 shows the voltammetric results of the oxygen reduction current value of platinum using Na f ion, CMC, and PVDF as the binder.
  • Figure 7 shows the correlation between voltammogram area Z specific surface area and overvoltage.
  • Voltammetry (vo 1 t amme try) measures the current while changing the voltage, creates a voltage-current curve (voltamgram), qualifies the target substance at the electrolytic potential, and the current value at that time This is a method for quantification. This means a method of measuring the current (amp e re) by regulating the potential (v o 1 t). Perform potential regulation voltammetry to measure the flowing current by changing the electrode potential with time.
  • the observed currents are a faradaic current based on the exchange of electrons by electrolysis and a capacitive current based on the temporal change in the capacitance due to adsorption of ionic molecules at the electrode interface.
  • Electrodes Various types of microelectrodes (mercury, platinum, gold, glassy carbon, etc.) are used as electrodes, and voltammetry is widely used for electrode reaction analysis, redox system research, and analysis of electrolyzed materials.
  • the potential of the indicating electrode is set to a specific value
  • the target substance is electrolytically deposited for a certain period of time
  • the substance is concentrated on the electrode, and then the electrode potential is set. Increase in the opposite direction and measure the current when the precipitated material elutes again.
  • Fig. 1 schematically shows how platinum atoms on the surface of platinum particles are oxidized by oxygen molecules generated from water molecules.
  • Fig. 2 shows an example of the Pt catalyst voltammogram (potential scanning speed 0.31 V / s) in 0.5 mo 1 1 H 2 SO 4 .
  • Many current peaks appear in the figure. So The electrode reaction occurring at each current peak is estimated as follows from the influence on the peak current value or peak current value, such as the change in potential scanning speed, the effect of stirring, and the change in pH. ing.
  • the voltammogram area could not be emphasized, and the difference in the oxide film was unclear.
  • the voltamgram area was standardized by improving the evaluation method of the voltammogram area and setting the voltamgram area to the Z catalyst specific surface area.
  • CMC and PVDF binder as the binder for voltammetry, the change in the voltammogram area was emphasized and the difference in the acid film could be clarified.
  • a known carbon material can be used for the conductive carrier used in the electrode catalyst for fuel cells of the present invention.
  • carbon black such as channel black, furnace black, thermal black, and acetylene black is preferably exemplified by activated carbon.
  • a fluorine-based electrolyte or a hydrocarbon-based electrolyte can be used as the polymer electrolyte.
  • a fluorine-based polymer electrolyte is one in which an electrolyte group such as a sulfonic acid group or a carboxylic acid group is introduced into a fluorine-based polymer compound.
  • the fluorine-based polymer electrolyte used in the fuel cell of the present invention is a polymer in which an electrolyte group such as a sulfonic acid group is introduced as a substituent in a fluorocarbon skeleton or a hydrofluorocarbon skeleton.
  • the hydrocarbon-based polymer electrolyte used in the fuel cell of the present invention is one having a hydrocarbon moiety in one of the molecular chains constituting the polymer compound and having an electrolyte group introduced.
  • examples of the electrolyte group include a sulfonic acid group and a carboxylic acid group.
  • Figure 3 shows that the gas flow rate is 12 mi at the canode, 6 mi at the power sword, the cell temperature is 80 ° C, the anode hubra temperature is 58 ° C, the cathode hubra temperature is 48 ° C, and the P t catalyst weight is 0.35 mgZ.
  • the current-voltage curve was determined as cm 2 .
  • the cell voltage of 0.9 V at a current density of 0 is 0.3 V less than the theoretical electromotive force of 1.2 V, and this value is excessive Iff.
  • FIG. 5 compares the oxygen reduction current value at 80 OmV of platinum using Na fion (trade name), CMC, and PVDF as binders. It can be seen that when CMC or PVDF is used as the binder, the reduction current value changes greatly.
  • FIG. 6 shows that Na fion (trade name), CMC, and P VDF were used as binders when each potential was applied in steps of 2 minutes at 0 2 _L SV @ 1600 rpm.
  • the results of voltammetry of the oxygen reduction current value of platinum used are shown. It can be seen that when PVDF is used as the binder, the oxygen reduction current value changes greatly.
  • Figure 7 shows the correlation between voltammogram area, catalyst specific surface area, and overvoltage. The vertical axis represents the cell voltage drop from the electromotive force as an overvoltage, and the horizontal axis represents the value obtained by dividing the voltammogram area obtained from the voltammetric analysis calculated by the present inventor by the specific surface area of the catalyst.
  • the surface of the air electrode catalyst eg, Pt catalyst
  • the cell voltage decreases (overvoltage increases).
  • a negative correlation between the specific surface area of the catalyst and the overvoltage was clearly seen. From the results shown in Fig. 7, it is necessary to reduce the overvoltage of the Nafion (trade name) based fuel cell catalyst to 0.4 V or less.
  • the voltammogram area and the specific surface area of the catalyst are 1.0 X 1 0— 4 mV ⁇ A ⁇ If g Zrn is 2 or higher, it will be good.
  • the present invention by dividing the voltammogram area of the electrocatalyst obtained from voltammetry by the specific surface area of the catalyst and normalizing it, it is used as an index for performance evaluation and search for a new catalyst. It is possible to accurately evaluate and search for battery electrode catalysts. This greatly reduces the labor and time required for fuel cell performance evaluation and search, and contributes to the practical application and spread of fuel cells.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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Abstract

La présente invention concerne un procédé pour évaluer les performances d'un catalyseur d'électrode destiné à une batterie de piles à combustible, comprenant un catalyseur métallique sur un support électro-conducteur. Dans le cadre du procédé d'évaluation, la valeur de l'aire de voltammogramme / de l'aire de surface spécifique de catalyseur dans le catalyseur d'électrode, est utilisée comme indice pour l'évaluation des performances, et lorsque cette valeur est supérieure ou égale à 1,0×10-4(mV A g/m2), les performances sont évaluées comme bonnes. Le procédé de l'invention permet d'évaluer correctement les performances du catalyseur d'électrode destiné à une batterie de piles à combustible. L'invention concerne également un procédé pour analyser un catalyseur d'électrode destiné à une batterie de piles à combustible, ayant des performances excellentes, et un nouveau catalyseur d'électrode destiné à une batterie de piles à combustible ayant une activité catalytique excellente, et analysé au moyen du procédé mentionné ci-dessus.
PCT/JP2007/061029 2006-05-24 2007-05-24 Procédé pour évaluer les performances d'un catalyseur d'électrode pour batterie, procédé pour analyser un catalyseur d'électrode pour batterie, catalyseur d'électrode pour batterie, et batterie de piles à combustible comprenant le catalyseur d'électrode WO2007136140A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP07744440A EP2031678A1 (fr) 2006-05-24 2007-05-24 Procédé pour évaluer les performances d'un catalyseur d'électrode pour batterie, procédé pour analyser un catalyseur d'électrode pour batterie, catalyseur d'électrode pour batterie, et batterie de piles à combustible comprenant le catalyseur d'électrode
US12/299,990 US20090117450A1 (en) 2006-05-24 2007-05-24 Method for evaluating performance of electrode catalyst for cell, search method, electrode catalyst for cell and fuel cell using same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006144305A JP2007317437A (ja) 2006-05-24 2006-05-24 電池用電極触媒の性能評価方法、探索方法、電池用電極触媒及びその電極触媒を用いた燃料電池
JP2006-144305 2006-05-24

Publications (1)

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WO2007136140A1 true WO2007136140A1 (fr) 2007-11-29

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US (1) US20090117450A1 (fr)
EP (1) EP2031678A1 (fr)
JP (1) JP2007317437A (fr)
CN (1) CN101454930A (fr)
WO (1) WO2007136140A1 (fr)

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US20100112401A1 (en) * 2007-03-01 2010-05-06 Hironori Noto Fuel cell system, electrode catalyst degradation judgment method, and moving body

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WO2010146712A1 (fr) * 2009-06-19 2010-12-23 トヨタ自動車株式会社 Système de pile à combustible
WO2011036765A1 (fr) * 2009-09-25 2011-03-31 トヨタ自動車株式会社 Système de pile à combustible
US8450020B2 (en) * 2011-04-26 2013-05-28 GM Global Technology Operations LLC In-vehicle algorithm for fuel cell stack health quantification
DE102012006131A1 (de) 2012-03-27 2012-09-27 Daimler Ag Verfahren zum Bestimmen der elektrochemisch aktiven Oberfläche eines katalytischen Materials
US11145874B2 (en) * 2017-04-18 2021-10-12 Tanaka Kikinzoku Kogyo K.K. Catalyst for solid polymer fuel cells and method for producing same
CN108134104B (zh) * 2017-12-26 2020-05-12 成都新柯力化工科技有限公司 一种燃料电池用复合催化剂载体及其制备方法和应用
KR102686557B1 (ko) * 2018-11-23 2024-07-19 한국재료연구원 연료전지 촉매층 성능평가용 셀 및 이를 이용한 연료전지 촉매층 성능평가 방법

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100112401A1 (en) * 2007-03-01 2010-05-06 Hironori Noto Fuel cell system, electrode catalyst degradation judgment method, and moving body
US8900768B2 (en) * 2007-03-01 2014-12-02 Toyota Jidosha Kabushiki Kaisha Fuel cell system, electrode catalyst degradation judgment method, and moving body

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JP2007317437A (ja) 2007-12-06
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EP2031678A1 (fr) 2009-03-04

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